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At least 919 records · Page 51

Supersonic combustor modeling

The physical phenomena involved when a supersonic flow undergoes chemical reaction are discussed. Detailed physical models of convective and diffusive mixing, and finite rate chemical reaction in supersonic flow are presented. Numerical algorithms used to solve the equations governing these processes are introduced. Computer programs using these algorithms are used to analyze the structure of the reacting mixing layer. It is concluded that, as in subsonic flow, exothermic heat release in unconfined supersonic flows retards fuel/air mixing. Non mixing is shown to be a potential problem in reducing the efficiency of supersonic as well as subsonic combustion. Techniques for enhancing fuel/air mixing and combustion are described.

Riggins, David W.↗

Gait Training Improves Performance in Healthy Adults Exposed to Novel Discordant Conditions

After they return to Earth, astronauts experience sensorimotor disturbances that disrupt their ability to walk. We have previously shown that training with a variety of sensorimotor adaptive challenges enhances the capability of adapting to novel sensorimotor conditions. We are currently developing a sensorimotor adaptability (SA) training program designed to facilitate recovery of function after gravitational transitions. The purpose of this study was to determine whether trained subjects could transfer learned skills from one discordant visuo-proprioceptive environment to another. During three sessions, subjects walked at 2.5 km/h on a treadmill mounted on a motion base platform. Ten subjects trained with a combination of lateral treadmill translation and superimposed sinusoidal lateral optic flow that was presented on a large screen positioned in front of them. Ten controls completed the same training schedule while viewing only the forward optic flow with no visual or physical oscillation. Twenty minutes after the final training session, all subjects completed a 2-minute trial with a novel combination of visual and treadmill roll perturbations not previously experienced during the training (Transfer Test). Compared to the untrained group, participants who received SA training showed faster reaction times and, based on a composite score derived from stride frequency, heart rate, and reaction time, an overall enhanced performance. Our results showed that an SA training program can improve overall walking performance when subjects are exposed to novel incongruent sensory environments. This training has application for both enhancing adaptive responses in astronauts and reducing fall and injury risk in the elderly.

Batson, Crystal D.↗

Oxidation Study of an Ultra High Temperature Ceramic Coatings Based on HfSiCN

High temperature fiber-reinforced ceramic matrix composites (CMCs) are important for aerospace applications because of their low density, high strength, and significantly higher-temperature capabilities compared to conventional metallic systems. The use of the SiCf/SiC and Cf/SiC CMCs allows the design of lighter-weight, more fuel efficient aircraft engines and also more advanced spacecraft airframe thermal protection systems. However, CMCs have to be protected with advanced environmental barrier coatings when they are incorporated into components for the harsh environments such as in aircraft engine or spacecraft applications. In this study, high temperature oxidation kinetics of an advanced HfSiCN coating on Cf/SiC CMC substrates were investigated at 1300 C, 1400 C, and 1500 C by using thermogravimetric analysis (TGA). The coating oxidation reaction parabolic rate constant and activation energy were estimated from the experimental results. The oxidation reaction studies showed that the coatings formed the most stable, predominant HfSiO4-HfO2 scales at 1400 C. A peroxidation test at 1400 C then followed by subsequent oxidation tests at various temperatures also showed more adherent scales and slower scale growth because of reduced the initial transient oxidation stage and increased HfSiO4-HfO2 content in the scales formed on the HfSiCN coatings.

Environmental Barrier Coatings↗

Oxidation Study of an Ultra High Temperature Ceramic Coatings Based on HfSiCN

High temperature fiber-reinforced ceramic matrix composites (CMCs) are important for aerospace applications because of their low density, high strength, and significantly higher-temperature capabilities compared to conventional metallic systems. The use of the SiCf/SiC and Cf/SiC CMCs allows the design of lighter-weight, more fuel efficient aircraft engines and also more advanced spacecraft airframe thermal protection systems. However, CMCs have to be protected with advanced environmental barrier coatings when they are incorporated into components for the harsh environments such as in aircraft engine or spacecraft applications. In this study, high temperature oxidation kinetics of an advanced HfSiCN coating on Cf/SiC CMC substrates were investigated at 1300 C, 1400 C, and 1500 C by using thermogravimetric analysis (TGA). The coating oxidation reaction parabolic rate constant and activation energy were estimated from the experimental results. The oxidation reaction studies showed that the coatings formed the most stable, predominant HfSiO4-HfO2 scales at 1400 C. A peroxidation test at 1400 C then followed by subsequent oxidation tests at various temperatures also showed more adherent scales and slower scale growth because of reduced the initial transient oxidation stage and increased HfSiO4-HfO2 content in the scales formed on the HfSiCN coatings.

Ultra High Temperature Ceramics (UHTC)↗

Oxidative vaporization kinetics of Cr2O3 in oxygen from 1000 to 1300 C

Rates of oxidative vaporization of Cr2O3 on preoxidized resistively heated chromium were determined in flowing oxygen at a pressure of 0.115 Torr for temperatures from 1000 to 1300 C. Reaction controlled rates were obtained from experimental rates by a gold calibration technique, and these rates were shown to agree with those predicted by thermochemical analysis. The activation energy obtained for the oxidative vaporization reaction corresponded numerically with the thermochemical enthalpy of the reaction. A theoretical equation is given for calculating the rate from thermodynamic data using boundary-layer theory.

Stearns, C. A.↗

Adiabaticity and nonadiabaticity in bimolecular outer-sphere charge transfer reactions

A model for outer-sphere bimolecular electron transfer reactions is presented which is based on a rate expression correct in the adiabatic, nonadiabatic, and intermediate dynamical regimes for an overdamped solvent coordinate. A complete discussion of the time-scale separations needed to define a bimolecular rate for these electron transfer reactions is given. Bimolecular reaction rates are predicted to display distinct solvent and electronic coupling dependencies, defined by a few experimentally variable parameters.

Beratan, David N.↗

Was Ferrocyanide a Prebiotic Reagent?

Hydrogen cyanide is the starting material for a diverse array of prebiotic syntheses, including those of amino acids and purines. Hydrogen cyanide also reacts with ferrous ions to give ferrocyanide, and so it is possible that ferrocyanide was common in the early ocean. This can only be true if the hydrogen cyanide concentration was high enough and the rate of reaction of cyanide with ferrous ions was fast enough. We show experimentally that the rate of formation of ferrocyanide is rapid even at low concentrations of hydrogen cyanide in the pH range 6-8, and therefore an equilibrium calculation is valid. The equilibrium concentrations of ferrocyanide are calculated as a function of hydrogen cyanide concentration, pH and temperature. The steady state concentration of hydrogen cyanide depends on the rate of synthesis by electric discharges and ultraviolet light and the rate of hydrolysis, which depends on pH and temperature. Our conclusions show that ferrocyanide was a major species in the prebiotic ocean only at the highest production rates of hydrogen cyanide in a strongly reducing atmosphere and at temperatures of 0 C or less, although small amounts would have been present at lower hydrogen cyanide production rates. The prebiotic application of ferrocyanide as a source of hydrated electrons, as a photochemical replication process, and in semi-permeable membranes is discussed.

Keefe, Anthony D.↗

Kinetic and Thermodynamic Characterization of the Cobalt and Manganese Oxyhydroxide Cores Formed in Horse Spleen Ferritin

Horse spleen ferritin (HoSF) containing 800-1500 cobalt or 250-1200 manganese atoms as Co(O)OH and Mn(O)OH mineral cores within the HoSF interior (Co-HoSF and Mn-HoSF) was synthesized, and the chemical reactivity, kinetics of reduction, and the reduction potentials were measured. Microcoulometric and chemical reduction of HoSF containing the M(O)OH mineral core (M = Co or Mn) was rapid and quantitative with a reduction stoichiometry of 1.05+/-0.10 e/M forming a stable M(OH)2 mineral core. At pH 9.0, ascorbic acid (AH2), a two-electron reductant, effectively reduced the mineral cores; however, the reaction was incomplete and rapidly reached equilibrium. The addition of excess AH2 shifted the reaction to completion with a M(3+)/AH2 stoichiometry of 1.9-2.1, consistent with a single electron per metal atom reduction. The rate of reaction between M(0)OH and excess AH2 was measured by monitoring the decrease in mineral core absorbance with time. The reaction was first order in each reactant with second-order rate constants of 0.53 and 4.74/M/min, respectively, for Co- and Mn-HoSF at pH 9.0. From the variation of absorbance with increasing AH2 concentration, equilibrium constants at pH 9.0 of 5.0+/-1.9 for Co-HoSF and 2.9+/-0.9 for Mn-HoSF were calculated for 2M(O)OH + AH2 = 2M(OH)2 f D, where AH2 and D are ascorbic acid and dehydroascorbic acid, respectively. Consistent with these equilibrium constants, the standard potential for the reduction of Co(III)-HoSF is 42 mV more positive than that of the ascorbic acid reaction, while the standard potential of Mn(III)-HoSF is 27 mV positive relative to AH2. Fe(2+) in solution with Co- and Mn-HoSF under anaerobic conditions was oxidized to form Fe(O)OH within the HoSF interior, resulting in partial displacement of the Co or Mn by iron.

Zhang, Bo↗

The reaction N/4S/ + O3 - An upper limit for the rate constant at 298 K

The reaction of N(4S) atoms with ozone was examined at 298 K using discharge flow and flash photolysis techniques, both coupled with resonance fluorescence detection of N(4S). No reaction was detected in either system, and an upper limit of 5 x 10 to the -16th cu cm/molecule/s was estimated for the rate constant. This is 1000 times lower than the presently accepted value of 5.7 x 10 to the -13th cu cm/molecule/s which is based on a discharge flow-mass spectrometric study of the reaction. Potential complications in the latter experiment are discussed.

Stief, L. J.↗

Rate constants measured for hydrated electron reactions with peptides and proteins

Effects of ionizing radiation on the amino acids of proteins and the reactivity of the protonated amino group depends upon the pK subscript a of the group. Estimates of the rate constants for reactions involving the amino acid side chains are presented. These rate constants gave an approximate rate constant for three different protein molecules.

Braams, R.↗

Temperature-Dependent Rate Constants and Substituent Effects for the Reactions of Hydroxyl Radicals With Three Partially Fluorinated Ethers

Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol.

Hsu, K.-J.↗

Rate constant for the OH + CO reaction - Pressure dependence and the effect of oxygen

The effect of pressure on the rate constant of the OH + CO reaction has been measured for Ar, N2, and SF6 over the pressure range 200-730 torr. All experiments were at room temperature. The method involved laser-induced fluorescence to measure steady-state OH concentrations in the 184.9 nm photolysis of H2O-CO mixtures in the three carrier gases, combined with supplementary measurements of the CO depletion in these same carrier gases in the presence and absence of competing reference reactants. The effect of O2 on the pressure effect was determined. A pressure enhancement of the rate constant was observed for N2 and SF6, but not for Ar, within an experimental error of about 10 percent. The pressure effect for N2 was somewhat lower than previous literature reports, being about 40 percent at 730 torr. For SF6 a factor of two enhancement was seen at 730 torr. In each case it was found that O2 had no effect on the pressure enhancement. The roles of the radical species HCO and HOCO were evaluated.

Demore, W. B.↗

Vibration computer programs E13101, E13102, E13104, and E13112 and application to the NERVA program. Project 187: Methodology documentation

Programs for the analyses of the free or forced, undamped vibrations of one or two elastically-coupled lumped parameter teams are presented. Bearing nonlinearities, casing and rotor distributed mass and elasticity, rotor imbalance, forcing functions, gyroscopic moments, rotary inertia, and shear and flexural deformations are all included in the system dynamics analysis. All bearings have nonlinear load displacement characteristics, the solution is achieved by iteration. Rotor imbalances allowed by such considerations as pilot tolerances and runouts as well as bearing clearances (allowing concail or cylindrical whirl) determine the forcing function magnitudes. The computer programs first obtain a solution wherein the bearings are treated as linear springs of given spring rates. Then, based upon the computed bearing reactions, new spring rates are predicted and another solution of the modified system is made. The iteration is continued until the changes to bearing spring rates and bearing reactions become negligibly small.

Mironenko, G.↗

Smoldering News From STS-77 Endeavour

The Microgravity Smoldering Combustion (MSC) experiment lifted off aboard the Space Shuttle Endeavour for its second flight in May 1996, as part of the STS-77 mission. This experiment is part of a series of studies focused on the smolder characteristics of porous combustible materials in a microgravity environment. Smoldering is a nonflaming form of combustion that takes place in the interior of combustible materials. Common examples of smoldering are nonflaming embers, charcoal briquettes, and cigarettes. The objective of this study is to provide a better understanding of the controlling mechanisms of smoldering in microgravity and normal Earth gravity (1g). As with other forms of combustion, gravity affects the availability of air and transport of heat, and therefore, the rate of combustion. The results of the microgravity experiments will be compared with identical ones carried out in 1g. In addition, they will be used to verify present theories of smolder combustion and will provide new insights into the process of smoldering combustion, enhancing our fundamental understanding of this frequently encountered combustion process and guiding improvements in fire safety practices. Two smoldering combustion tests with polyurethane foam were successfully accomplished during the STS-77 mission. The tests investigated smoldering combustion in a quiescent (no-flow) enriched oxygen environment, and in an air environment with a 2-mm/sec airflow through the fuel sample. The primary data from the tests are the ignition characteristics, spread rate, smolder reaction temperature, and products of combustion (solid and gas). On both the first mission on STS-69 and the second mission on STS-77, a smolder front propagated the length of the forced-flow samples, with the spread rate between the corresponding upward and downward 1g smolder rates. Neither of the quiescent cases propagated combustion (the first case was due in part to a problem with the experiment electronics). These results show a dramatic difference from the normal gravity results, where smolder propagation is very rapid and complete for both of these conditions. The experiment was conceived by Prof. A. Carlos Fernandez-Pello at the University of California-Berkeley. The MSC hardware was designed and built at the NASA Lewis Research Center by a team of civil servants and contractors from NYMA, Inc., and Aerospace Design & Fabrication, Inc. (ADF). The hardware consists of two sealed aluminum combustion chambers (each being a half a cylinder). The chambers hold the MSC test section, data acquisition electronics, power distribution electronics, and instrumentation. The hardware is fitted into a 5-ft(sup 3) Get-Away-Special (GAS) canister that is mounted in the shuttle cargo bay. The test section consists of a quartz cylinder that contains the polyurethane foam sample and an igniter. This igniter, which is an electrically heated wire sandwiched between two porous ceramic disks, is mounted in contact with the end of the foam sample. An array of 12 thermocouples placed axially and radially along the foam sample provide temperature histories, which are used to determine the rate of smolder propagation, and the characteristics of the reaction.

Koudelka, John M.↗

Universal Responses of Cyclic-Oxidation Models Studied

Oxidation is an important degradation process for materials operating in the high-temperature air or oxygen environments typical of jet turbine or rocket engines. Reaction of the combustion gases with the component material forms surface layer scales during these oxidative exposures. Typically, the instantaneous rate of reaction is inversely proportional to the existing scale thickness, giving rise to parabolic kinetics. However, more realistic applications entail periodic startup and shutdown. Some scale spallation may occur upon cooling, resulting in loss of the protective diffusion barrier provided by a fully intact scale. Upon reheating, the component will experience accelerated oxidation due to this spallation. Cyclic-oxidation testing has, therefore, been a mainstay of characterization and performance ranking for high-temperature materials. Models simulate this process by calculating how a scale spalls upon cooling and regrows upon heating (refs. 1 to 3). Recently released NASA software (COSP for Windows) allows researchers to specify a uniform layer or discrete segments of spallation (ref. 4). Families of model curves exhibit consistent regularity and trends with input parameters, and characteristic features have been empirically described in terms of these parameters. Although much insight has been gained from experimental and model curves, no equation has been derived that can describe this behavior explicitly as functions of the key oxidation parameters.

Smialek, James L.↗